High efficiency, high temperature catalyst for polymerizing olefins

ABSTRACT

Compositions exhibiting high catalytic activity in the polymerization of α-olefins at temperatures above 140° C. are provided by reacting a transition metal compound such as tetra(isopropoxy)titanium, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum, e.g., di-n-butylmagnesium.x triethylaluminum and a hydrogen halide or an active hydrocarbyl halide such as t-butyl chloride. Polymerization processes employing this catalyst composition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 765,182, filed Feb. 3, 1977,now U.S. Pat. No. 4,250,288, which is a continuation-in-part ofapplication Ser. No. 581,294 filed May 27, 1975, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to a new catalyst composition useful forinitiating and promoting polymerization of α-olefins and to apolymerization process employing such a catalyst composition.

It is well known that olefins such as ethylene, propylene, and 1-butenein the presence of metallic catalysts, particularly the reactionproducts of organometallic compounds and transition metal compounds canbe polymerized to form substantially unbranched polymers of relativelyhigh molecular weight. Typically such polymerizations are carried out atrelatively low temperatures and pressures.

Among the methods for producing such linear olefin polymers, some of themost widely utilized are those described by Professor Karl Ziegler inU.S. Pat. Nos. 3,113,115 and 3,257,332. In these methods, the catalystemployed is obtained by admixing a compound of a transition metal ofGroups 4b, 5b, 6b and 8 of Mendeleev's Periodic Table of Elements withan organometallic compound. Generally, the halides, oxyhalides andalkoxides or esters of titanium, vanadium and zirconium are the mostwidely used transition metal compounds. Common examples of theorganometallic compounds include the hydrides, alkyls and haloalkyls ofaluminum, alkylaluminum halides, Grignard reagents, alkali metalaluminum hydrides, alkali metal borohydrides, alkali metal hydrides,alkaline earth metal hydrides and the like. Usually, polymerization iscarried out in a reaction medium comprising an inert organic liquid,e.g., an aliphatic hydrocarbon and the aforementioned catalyst. One ormore olefins may be brought into contact with the reaction medium in anysuitable manner, and a molecular weight regulator, which is normallyhydrogen, is usually present in the reaction vessel in order to suppressthe formation of undesirably high molecular weight polymers.

Following polymerization, it is common to remove catalyst residues fromthe polymer by repeatedly treating the polymer with alcohol or otherdeactivating agent such as aqueous base. Such catalyst deactivationand/or removal procedures are expensive both in time and materialconsumed as well as the equipment required to carry out such treatment.

Furthermore, most of the aforementioned known catalyst systems are moreefficient in preparing polyolefins in slurry (i.e., wherein the polymeris not dissolved in the carrier) than in solution (i.e., wherein thetemperature is high enough to solubilize the polymer in the carrier).The lower efficiencies of such catalysts in solution polymerization isgenerally believed to be caused by the general tendency of suchcatalysts to become rapidly depleted or deactivated by significantlyhigher temperatures that are normally employed in solution processes.

Recently, catalysts having higher efficiencies have been disclosed,e.g., U.S. Pat. No. 3,392,159, U.S. Pat. No. 3,737,393, West GermanPatent Application No. 2,231,982 and British Pat. Nos. 1,305,610 and1,358,437. While the increased efficiencies achieved by using theserecent catalysts are significant, even higher efficiencies are desirablein order to more effectively control the polymerization atpolymerization temperatures above 140° C. and the products made thereby.

In view of the foregoing problems encountered in the use of conventionalZiegler catalysts, it would be highly desirable to provide apolymerization catalyst which is sufficiently active, even at solutionpolymerization temperatures above 140° C., to produce such highquantities of polymer per unit of catalyst that it is no longernecessary to remove catalyst residue in order to obtain a polymer of thedesired purity.

SUMMARY OF THE INVENTION

The present invention, in one aspect, is the catalytic reaction productof (A) a compound of a transition metal (TM), (B) an organomagnesiumcomponent and (C) a non-metallic monohalide. The magnesium component is(1) a complex of an organomagnesium compound and an organometalliccompound such as an alkylaluminum compound which solubilizes theorganomagnesium compound in hydrocarbon or (2) an organomagnesiumcompound. The non-metallic halide corresponds to the formula R'X whereinR' is hydrogen or an active monovalent organic radical and X is halogen.Furthermore, the catalytic reaction product contains a sufficientproportion of aluminum in the form of a hydrocarbyl aluminum compoundrepresented by the formula R_(3-a) AlX_(a) wherein R is hydrocarbyl, Xis halide and a is a number from 0 to 1. The proportions of theforegoing components of said catalytic reaction products are such thatthe atomic ratio of Mg:TM is from about 5:1 to about 2000:1, the atomicratio of X:TM is within the range from about 50:1 to about 2000:1, theatomic ratio of Mg:X is within the range from about 0.1:1 to about 1:1,the atomic ratio of Mg:Al is at least about 0.3:1 and the atomic ratioof Al:TM is not more than about 120:1.

In a second aspect, the invention is a process for polymerizing anα-olefin under conditions characteristic of Ziegler polymerizationwherein the aforementioned reaction product is preferably employed asthe sole catalyst.

In view of the reduced activity of conventional Ziegler catalysts atpolymerization temperatures above 140° C., it is indeed surprising thatthe aforementioned catalytic reaction product is a high efficiencycatalyst capable of producing more than a million pounds of olefinpolymer per pound of transition metal at polymerization temperaturesgreater than 150° C., e.g., from 185° to 220° C. and higher.Accordingly, olefin polymers produced in accordance with the foregoingprocess generally contain lower amounts of catalyst residues thanpolymers produced in the presence of conventional catalysts even aftersubjecting such polymers to catalyst removal treatments. Further, thesecatalytic reaction products enable a higher degree of control over thepolymerization in order that a more uniform product can be made.Additionally, the polymer produced in the practice of the presentinvention has a very narrow molecular weight distribution and istherefore highly useful in molding applications such as injectionmolding, film application and rotational molding.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is most advantageously practiced in apolymerization process wherein an α-olefin is polymerized, generally inthe presence of hydrogen as a molecular weight control agent, in apolymerization zone containing an inert diluent and the reaction productas hereinbefore described. The foregoing polymerization process is mostbeneficially carried out under inert atmosphere and relatively lowtemperature and pressure, although very high pressures are optionallyemployed.

Olefins which are suitably polymerized or copolymerized in the practiceof this invention are generally the aliphatic α-monoolefins having from2 to 18 carbon atoms. Illustratively, such α-olefins can includeethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1,octene-1, dodecene-1, octadecene-1 and the like. It is understood thatα-olefins may be copolymerized with other α-olefins and/or with smallamounts, i.e., up to about 10 weight percent based on the polymer, ofother ethylenically unsaturated monomers such as butadiene, isoprene,pentadiene-1,3, styrene, α-methylstyrene and similar ethylenicallyunsaturated monomers which do not destroy conventional Zieglercatalysts. Most benefits are realized in the polymerization of aliphaticα-monoolefins, particularly ethylene and mixtures of ethylene and up to10, especially from about 0.1 to about 5, weight percent of propylene,butene-1 or similar higher α-olefin based on total monomer.

Advantageously, the novel catalyst composition of the present inventionis the reaction product of (A) a compound of a transition metal(hereinafter called "TM") of Groups 4b, 5b, 6b, 7b and 8 of Mendeleev'sPeriodic Table of Elements as shown in The Chemical Rubber Company'sHandbook of Chemistry and Physics, 48th edition, and (B) an intermediatereaction product of (a) a hydrocarbon soluble organomagnesium compoundor a hydrocarbon soluble complex of an organomagnesium compound and anorganometallic compound having the formula MR_(y) wherein M is a metalof Groups 2b, 3a including boron, 1a, 4a including silicon; R is amonovalent hydrocarbon radical, i.e., hydrocarbyl, such as alkyl,cycloalkyl, alkenyl, aryl, arylalkyl and alkylaryl, or other monovalentorganic radical such as alkoxy, aryloxy, alkoxyalkyl, and the like; andy is a number corresponding to the valence of M, and (b) an activenon-metallic halide corresponding to the formula R'X wherein R' ishydrogen or hydrocarbyl such as alkyl, aryl and that are at least asactive as sec-butyl and X is halogen, preferably chloride, bromide, andiodide. It is understood that the organic moieties of the aforementionedcatalyst components, e.g., R and R', are suitably any other organicradical provided that they do not contain functional groups that poisonconventional Ziegler catalysts. Preferably such organic moieties do notcontain active hydrogen, i.e., those sufficiently active to react withthe Zerewitinoff reagent. The foregoing catalyst composition has anatomic ratio of Mg:TM in the range from about 5:1 to about 2000:1,preferably from about 10:1 to about 200:1, most preferably from about10:1 to about 60:1; an atomic ratio of Mg:X in the range from about0.1:1 to about 1:1, preferably from about 0.2:1 to about 0.7:1, mostpreferably from about 0.4:1 to 0.6:1; and an atomic ratio of X:TM in therange from about 40:1 to about 2000:1, preferably from about 50:1 toabout 400:1, most preferably from about 60:1 to about 120:1.Furthermore, the catalytic reaction product contains sufficient R_(3-a)AlX_(a) as defined hereinbefore (preferably wherein R is alkyl, X is Clor Br and a is 0 to 1) to provide an atomic ratio of Mg:Al of at least0.3:1, preferably from about 0.5:1 to about 10:1, more preferably fromabout 0.6:1 to about 7:1 and an atomic ratio of Al:TM less than about120:1, preferably less than about 40:1.

Of the suitable transition metal compounds, those of titanium, vanadium,zirconium are more advantageously employed, with those of titanium beingmost advantageous. Beneficial compounds are the halides, oxyhalides,hydrocarbyloxides (e.g. alkoxides) amides acetylacetonates, alkyls,aryls, alkenyls, and alkadienyls. Of the foregoing transition metalcompounds, the hydrocarbyloxides of titanium, so-called titanates, arethe most beneficial.

Of the titanates, preferred ones are alkoxides or aryloxides, especiallyalkoxides having from 1 to 12 carbon atoms or a phenoxide, of trivalentor tetravalent titanium. Such titanates are preferably derived fromhalides of trivalent or tetravalent titanium including alkyl titaniumhalides wherein one or more halogen atoms are replaced by an alkoxy oraryloxy group. Exemplary preferred titanates includetetrabutoxytitanium, tetra(isopropoxy)titanium, diethoxytitaniumbromide, dibutoxytitanium dichloride, n-butyltriisopropoxytitanium,ethyl dibutoxytitanium chloride, monoethoxytitanium trichloride,tetraphenoxytitanium and the like. Of the preferred titanates, thetetravalent ones wherein all halogen atoms are replaced by alkoxide aremost preferred, with tetra(isopropoxy)titanium and tetrabutoxytitaniumbeing especially preferred.

Examples of other transition metal compounds which are advantageouslyemployed are titanium tetrachloride, titanium trichloride, vanadiumtrichloride, vanadium tetrachloride, vanadium oxychloride, zirconiumtetrachloride, titanocene dichloride, zirconium tetraalcoholates such astetrabutoxyzirconium, vanadium acetylacetonate and the like.

The preferred organomagnesium complex is a hydrocarbon soluble complexillustrated by the formula MgR₂.xMR_(y) wherein R is hydrocarbyl, M isaluminum, zinc or mixtures thereof and x is about 0.001 to 10 (usuallyfrom 0.001 to 3. when M is Al) and y denotes the number of hydrocarbylgroups which corresponds to the valence of M. When the organometalliccompound (MR_(y)) is an aluminum compound, it is desirable to maintainthe atomic ratios of Mg:Al and Al:TM within the ranges specifiedhereinbefore. In order to obtain maximum catalyst efficiency atpolymerization temperatures above 180° C., it is desirable to minimizethe amount of aluminum in the complex as well as in the total catalystso that the atomic ratio of Al:TM in the total catalytic reactionproduct is less than about 40:1.

This complex is prepared by reacting particulate magnesium such asmagnesium turnings or magnesium particles with about a stoichiometricamount of hydrocarbyl halide, illustrated as RX. The resultinghydrocarbon insoluble MgR₂ is then solubilized by adding theorganometallic compound such as AlR₃ or mixtures thereof with ZnR₂. Whenemploying a mixture of AlR₃ and ZnR₂ to solubilized MgR₂, the atomicratio of Zn to Al is from about 3000:1 to about 0.01:1, preferably fromabout 350:1 to about 1:1. The amount of organometallic compound which isadded to the MgR₂ to form the organomagnesium complex should be enoughto solubilize a significant amount of MgR₂, e.g., at least 5 weightpercent of MgR₂ is solubilized. It is preferred to solubilize at least50 weight percent of the MgR₂ and especially preferred to solubilize allof MgR₂.

In suitable complexes, organometallic compounds (other than AlR₃, ZnR₂or mixtures thereof) which also solubilize the organomagnesium compoundin hydrocarbon are employed in beneficial amounts, usually an amountsufficient to produce an atomic ratio of 0.01:1 to 10:1 of metal of theorganometallic compound to magnesium. Examples of such otherorganometallic compounds include boron trialkyls such as boron triethyl,alkyl silanes such as dimethyl silane and tetraethyl silane.

Alternative to the aforementioned hydrocarbon soluble complexes, it isalso advantageous to employ organomagnesium compounds as theorganomagnesium component. Such compounds, although conventionallyinsoluble in hydrocarbon, are suitably employed. These compounds can berendered soluble in hydrocarbon by addition of ether, amine, etc.,although such solubilizing agents often reduce the activity of thecatalyst. Recently, such compounds have been made hydrocarbon solublewithout using such catalyst poisons, e.g., as taught in U.S. Pat. No.3,646,231. The more recent hydrocarbon solubilized organomagnesiumcompounds are the most desirable if an organomagnesium compound is to beused as the organomagnesium component.

Preferably the organomagnesium compound is dihydrocarbylmagnesium suchas the magnesium dialkyls and the magnesium diaryls. Exemplary suitablemagnesium dialkyls include dibutylmagnesium, dipropylmagnesium,diethylmagnesium, dihexylmagnesium, propylbutylmagnesium and otherswherein alkyl has from 1 to 20 carbon atoms. Exemplary suitablemagnesium diaryls include diphenylmagnesium, dibenzylmagnesium, andditolylmagnesium, with the dialkylmagnesiums such as dibutylmagnesium,being especially preferred. Suitable organomagnesium compounds includealkyl and aryl magnesium alkoxides and aryloxides and aryl and alkylmagnesium halides with the halogen-free organomagnesium compounds beingmore desirable.

In cases wherein the organomagnesium component does not containaluminum, it is desirable to add a small proportion of an aluminumcompound during the preparation of the catalytic reaction product inorder to provide the desired Mg:Al and Al:TM ratios specifiedhereinbefore. Such aluminum compounds which may be added include alkylaluminum compounds, e.g., a trialkyl aluminum, an alkyl aluminum halideor an aluminum halide. However, when the aluminum compound added isalkyl aluminum dihalide or aluminum halide, steps should be taken thatthe catalytic reaction product be substantially free of R_(3-b) AlX_(b)wherein b=1.5 or more. Preferably, the catalytic reaction productcontains less than 5 weight percent of R_(3-b) AlX_(b), most preferablyless than about 1 weight percent, based on the weight of total aluminumcompound.

The active non-metallic halides of the formula set forth hereinbeforeinclude hydrogen halides and active organic halides such as t-alkylhalides, allyl halides, benzyl halides and other active hydrocarbylhalides wherein hydrocarbyl is a monovalent hydrocarbon radical. By anactive organic halide is meant a hydrocarbyl halide that contains alabile halogen at least as active, i.e., easily lost to anothercompound, as the halogen of sec-butyl chloride, preferably as active ast-butyl chloride. In addition to the organic monohalides, it isunderstood that organic dihalides, trihalides and other polyhydridesthat are active as defined hereinbefore are also suitably employed.

Examples of preferred active halides include hydrogen chloride, hydrogenbromide, t-butyl chloride, t-amyl bromide, allyl chloride, benzylchloride, crotyl chloride, methylvinyl carbinyl chloride, α-phenylethylbromide, diphenyl methyl chloride and the like. Most preferred arehydrogen chloride, t-butyl chloride, allyl chloride, and benzylchloride.

The organomagnesium component is preferably reacted in hydrocarbon withthe active non-metallic halide by adding with stirring the halide to thehydrocarbon containing the organomagnesium component. Alternatively,this desired intermediate reaction product may be formed by adding withstirring the organomagnesium component to the active halide or bysimultaneously adding and mixing the halide and the organomagnesiumcomponent over a period of time. The reaction between theorganomagnesium component and the active halide causes the formation ofa finely divided insoluble material. This intermediate reaction productcontains hydrocarbon soluble portions as well as hydrocarbon insolubleportions. In preferred embodiments, essentially all (preferably 100weight percent) of the organomagnesium compound is converted to ahydrocarbon insoluble solid. The amount of the halide added to theorganomagnesium component is sufficient to provide an atomic ratio ofMg:X as set forth hereinbefore. However, the amount of halide should notbe in such amounts and/or in such a manner as to produce significantamounts of R_(3-b) AlX_(b) as defined hereinbefore.

The aforementioned intermediate reaction product is then advantageouslymixed with an amount of the transition metal compound, preferably byadding the transition metal compound to the intermediate reactionproduct, sufficient to provide a catalytic reaction product having anatomic ratio of X:TM and Mg:TM as indicated hereinbefore.

While the catalytic reaction product prepared in the foregoing manner isespecially preferred in the practice of this invention, a beneficialcatalytic reaction product can be prepared by mixing the activenon-metallic halide with the transition metal compound to form anintermediate reaction product thereof and subsequently reacting thisintermediate product with the organomagnesium complex. Also suitable,but less preferred, catalytic reaction products can be made by firstmixing the organomagnesium complex with the transition metal compoundand then adding the active non-metallic halide or by adding and mixingall three components simultaneously.

In the preparation of the foregoing catalytic reaction products, it ispreferred to carry out such preparation in the presence of an inertdiluent. The concentrations of catalyst components are preferably suchthat when the active non-metallic halide, and the magnesium complex arecombined, the resultant slurry is from about 0.005 to about 0.1 molar(moles/liter) with respect to magnesium. By way of an example ofsuitable inert organic diluents can be mentioned liquefied ethane,propane, isobutane, n-butane, n-hexane, the various isomeric hexanes,isooctane, paraffinic mixtures of alkanes having from 8 to 9 carbonatoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane,industrial solvents composed of saturated or aromatic hydrocarbons suchas kerosene, naphthas, etc., especially when freed of any olefincompounds and other impurities, and especially those having boilingpoints in the range from about -50° to about 200° C. Also included assuitable inert diluents are benzene, toluene, ethylbenzene, cumene,decalin and the like.

Mixing of the catalyst components to provide the desired catalyticreaction product is advantageously carried out under an inert atmospheresuch as nitrogen, argon or other inert gas at temperatures in the rangefrom about -50° to about 150° C., preferably from about 0° to about 50°C. The period of mixing is not considered to be critical as it is foundthat a sufficient catalyst composition most often occurs within about 1minute or less. In the preparation of the catalytic reaction product, itis not necessary to separate hydrocarbon soluble components fromhydrocarbon insoluble components of the reaction product. Further it isnot required to add a cocatalyst or an activator such as an alkylaluminum compound to the catalytic reaction product in order to obtain ahigh efficiency catalyst. In fact, it is generally undesirable to addany aluminum compound in excess of the amounts prescribed hereinbeforein order to retain high catalyst efficiency at high polymerizationtemperatures.

In the polymerization process employing the aforementioned catalyticreaction product, polymerization is effected by adding a catalyticamount of the above catalyst composition to a polymerization zonecontaining α-olefin monomer, or vice versa. The polymerization zone ismaintained at temperatures in the range from about 0° to about 300° C.,preferably at solution polymerization temperatures, e.g., from about150° to about 250° C. for a residence time of about 10 minutes toseveral hours, preferably 15 minutes to 1 hour. It is generallydesirable to carry out the polymerization in the absence of moisture andoxygen and a catalytic amount of the catalytic reaction product isgenerally within the range from about 0.0001 to about 0.01milligram-atoms transition metal per liter of diluent. It is understood,however, that the most advantageous catalyst concentration will dependupon polymerization conditions such as temperature, pressure, solventand presence of catalyst poisons and that the foregoing range is givento obtain maximum catalyst yields. Generally in the polymerizationprocess, a carrier which may be an inert organic diluent or solvent orexcess monomer is generally employed. In order to realize the fullbenefit of the high efficiency catalyst of the present invention, caremust be taken to avoid oversaturation of the solvent with polymer. Ifsuch saturation occurs before the catalyst becomes depleted, the fullefficiency of the catalyst is not realized. For best results, it ispreferred that the amount of polymer in the carrier not exceed about 50weight percent based on the total weight of the reaction mixture.

It is understood that inert diluents employed in the polymerizationrecipe are suitably as defined as hereinbefore.

The polymerization pressures preferably employed are relatively low,e.g., from about 100 to about 500 psig. However, polymerization withinthe scope of the present invention can occur at pressures fromatmospheric up to pressures determined by the capabilities of thepolymerization equipment. During polymerization it is desirable to stirthe polymerization recipe to obtain better temperature control and tomaintain uniform polymerization mixtures throughout the polymerizationzone.

In order to optimize catalyst yields in the polymerization of ethylene,it is preferable to maintain an ethylene concentration in the solvent inthe range from 1 to 10 weight percent, most advantageously 1.2 to 2weight percent. To achieve this when an excess of ethylene is fed intothe system, a portion of the ethylene can be vented.

Hydrogen is often employed in the practice of this invention to lowermolecular weight of the resultant polymer. For the purpose of thisinvention, it is beneficial to employ hydrogen in concentrations rangingfrom about 0.001 to about 1 mole per mole of monomer. The larger amountsof hydrogen within this range are found to produce generally lowermolecular weight polymer. It is understood that hydrogen can be addedwith a monomer stream to the polymerization vessel or separately addedto the vessel before, during or after addition of the monomer to thepolymerization vessel, but during or before the addition of thecatalyst.

The monomer or mixture of monomers is contacted with the catalyticreaction product in any conventional manner, preferably by bringing thecatalytic reaction product and monomer together with intimate agitationprovided by suitable stirring or other means. Agitation can be continuedduring polymerization, or in some instances the polymerization can beallowed to remain unstirred while polymerization takes place. In thecase of more rapid reactions with more active catalysts, means can beprovided for refluxing monomer and solvent, if any of the latter ispresent and thus remove the heat of reaction. In any event, adequatemeans should be provided for dissipating the exothermic heat ofpolymerization. If desired, the monomer can be brought in the vaporphase into contact with the catalytic reaction product, in the presenceor absence of liquid material. The polymerization can be effected in thebatch manner, or in a continuous manner, such as, for example, bypassing the reaction mixture through an elongated reaction tube which iscontacted externally with suitable cooling medium to maintain thedesired reaction temperature, or by passing the reaction mixture throughan equilibrium overflow reactor or a series of the same.

The polymer is readily recovered from the polymerization mixture bydriving off unreacted monomer and solvent if any is employed. No furtherremoval of impurities is required. Thus, a significant advantage of thepresent invention is the elimination of the catalyst residue removalsteps. In some instances, however, it may be desirable to add a smallamount of a catalyst deactivating reagent. The resultant polymer isfound to contain insignificant amounts of catalyst residue and topossess a very narrow molecular weight distribution.

The following examples are given to illustrate the invention, and shouldnot be construed as limiting its scope. All parts and percentages are byweight unless otherwise indicated.

GENERAL OPERATING PROCEDURE FOR WORKING EXAMPLES

In the following examples the catalyst preparations are carried out inthe absence of oxygen or water in a nitrogen filled gloved box. Thecatalyst components are used as diluted solutions in either n-heptane orIsopar E® (a mixture of saturated isoparaffins having 8 to 9 carbonatoms). The polymerization reactions are carried out in a five-literstainless steel stirred batch reactor at 150° C. unless otherwisestated. In such polymerization reactions two liters of dry oxygen-freeIsopar E® are added to the reactor and heated to 150° C. The reactor isvented to about 25 psig and 15 to 20 psi of hydrogen is added forpolymer molecular weight control. Then, 120 psi of ethylene is added tothe reactor and the ethylene pressure is set to maintain the reactorpressure at 155 to 165 psig. The catalyst is then pressured into thereactor using nitrogen and the reactor temperature is maintained for thedesired polymerization time. The polymerization reactor contents aredumped into a stainless steel beaker and allowed to cool. The resultingslurry is filtered and the polymer dried and weighed. The ethyleneconsumption during polymerization is recorded with a DP cell which showsthe rate of polymerization and the amount of polymer produced. Catalystefficiencies are reported as grams of polyethylene catalyst per gram oftitanium, g.PE/g.Ti.

EXAMPLE 1

A catalyst is prepared by adding with stirring 0.946 ml of 0.519 Mdi(n-butyl)magnesium.2 triethylaluminum to a solution of 15 ml of 0.123M anhydrous hydrogen chloride in Isopar E®. A white precipitate resultsimmediately upon addition of the magnesium complex. To the resultantslurry are added 1.18 ml of 0.01 M tetra(isopropoxy)titanium and 82.9 mlof Isopar E®. A 12.7-ml aliquot (0.0015 mmole Ti) of this catalyst isadded to the polymerization reactor producing an increase in temperatureto 167° C. After 30 minutes, 230 grams of linear polyethylene is formedto give a catalyst efficiency of 3.2×10⁶ g.PE/g.Ti.

EXAMPLE 2

A catalyst is prepared by adding 93 ml of Isopar E®, 2.5 ml of 1.15 Mt-butylchloride in Isopar E®, 3.05 ml of 0.295 M di(n-butyl)magnesium.2triethylaluminum to a 4 oz. bottle. To the resultant slurry is added 1.5ml of 0.01 M tetra(isopropoxy)titanium. Ten milliliters of this catalyst(0.0015 mmole Ti) is added to the polymerization reactor and after 30minutes the reactor contents are dumped. The yield of polymer is 204grams indicating a catalyst efficiency of 2.8×10⁶ g.PE/g.Ti.

EXAMPLE 3

To 247 pounds of Isopar E® is added 133 pounds of 0.516 Mdi(n-butyl)magnesium.2 aluminum triethyl complex. An 11.75-lb. portionof hydrogen chloride gas is added to the foregoing solution of thecomplex with agitation. The resultant slurry is cooled to ambienttemperature (˜25° C.) and 322 ml of neat tetra(isopropoxy)titanium isadded. The resulting catalyst is diluted with Isopar E® to give 500pounds of total catalyst. This catalyst is added continuously to a6900-gallon reactor along with 40,000 lbs/hr of ethylene and Isopar E®.The amounts of catalyst and Isopar E® are varied to maintain a reactortemperature of at least 185° C. Hydrogen is added to the reactor tocontrol molecular weight of the polymer such that the polymer has a MeltIndex of 2.5 to 12 decigrams per minute as determined by ASTM D-1238-65T(Condition E). The catalyst efficiency of the foregoing polymerizationis greater than 1×10⁶ g.PE/g.Ti.

EXAMPLE 4

To establish the improved stability of the present catalyst at hightemperature, three runs are carried out employing catalysts which differonly as to source of halide and concentration of aluminum.

In accordance with the present invention, a catalyst is prepared byadding to 30.16 Kg. of Isopar E® the following components:

311.85 g. of HCl gas

5.556 Kg. of 0.548 M DBMg.2ATE* in Isopar E®

29.6 mols. (28.27 g.) of neat tetra(isopropoxy)titanium

The resulting catalyst has an atomic ratio as follows:

    Cl/Mg/Al/Ti=90/31.5/59.5/1.

Following the general polymerization procedure in a 250-gallon stirredreaction vessel set hereinbefore except employing a polymerizationtemperature of 185° C., the foregoing catalyst exhibits a catalystefficiency of 1.07×10⁶ g.PE/g.Ti.

For purposes of comparison, a catalyst is prepared by adding to 25.54Kg. of Isopar E® the following components:

6.01 Kg. of 15 percent ethylaluminum dichloride in Isopar E®

6.69 Kg. of 0.548 M DBMg.2ATE* in Isopar E®

31.5 mols. (30.08 g.) neat tetra(isopropoxy)titanium.

The resulting catalyst has an atomic ratio as follows:

    Cl/Mg/Al/Ti=134/40/147/1

Again following the foregoing general polymerization procedure exceptfor polymerization temperature two runs using this catalyst are carriedout at polymerization temperatures of 150° C. and 170° C. In these runs,the catalyst exhibits catalyst efficiencies of 1.16×10⁶ g.PE/g.Ti and0.43×10⁶ g.PE/g.Ti, respectively. In a similar run wherein apolymerization temperature of 185° C. is employed, no measurable amountof polyethylene is produced.

EXAMPLE 5

As evidence of preferred order of addition of components in catalystpreparation, three runs are carried out under similar conditions exceptthat the order of addition of components in preparation of the catalystdiffers from one run to another. The components of the catalyst are asfollows:

0.0657 g. of HCl in 15 mls. of Isopar E®

0.1726 g. of 0.51 M DBMg.2ATE* in Isopar E®

0.0039 g. of neat tetra(isopropoxy)titanium.

Atomic ratio of the components is

    Cl/Mg/Al/Ti=130/40/80/1.

Polymerization is carried out according to the procedure of Example 4using a polymerization temperature of 150° C. The results are recordedin Table I.

                  TABLE I                                                         ______________________________________                                                                    Catalyst                                          Run                         Efficiency, (2)                                   No.    Order of Addition (1)                                                                              g . PE/g . Ti                                     ______________________________________                                        1      HCl/DBMg . 2ATE*/Ti(OiPr).sub.4                                                                     2.0 × 10.sup.6                             2      HCl/Ti(OiPr).sub.4 /DBMg . 2ATE*                                                                   0.98 × 10.sup.6                             3      DBMg . 2ATE*/Ti(OiPr).sub.4 /HCl                                                                   0.68 × 10.sup.6                             ______________________________________                                         (1) Components added to the catalyst reaction vessel in left to right         order. In Run No. 3, the mixture of DBMg . 2ATE* + Ti(OiPr).sub.4 is adde     to HCl in Isopar E®.                                                      (2) Catalyst efficiency in grams of polyethylene per gram of titanium.        *di(nbutyl)magnesium . 2 aluminum triethyl                               

EXAMPLE 6

To illustrate the relation between Al:Ti and Al:Mg ratios and catalystefficiencies as temperature increases, several runs are carried outusing different proportions of the following catalyst components:

anhydrous HCl

DBMg.x ATE*

tetra(isopropoxy)titanium

in Isopar E®. The ratios of the foregoing catalyst components are shownin Table II.

Following the polymerization procedure of Example 4 at a polymerizationtemperature as indicated in Table II, ethylene is polymerized in thepresence of the several catalysts and the results are shown in Table II.

                  TABLE II                                                        ______________________________________                                                                          Catalyst                                    Run    Atomic Ratio,                                                                             Polymerization Efficiency,                                 No.    Cl/Mg/Al/Ti Temperature, °C.                                                                      g . PE/g . Ti                               ______________________________________                                        1      134/40/58/1 185            1.8 × 10.sup.6                        2      90/40/58/1  185            1.0 × 10.sup.6                        3      90/40/40/1  189            1.0 × 10.sup.6                        4      90/40/20/1  196            1.0 × 10.sup.6                        5      90/40/13.3/1                                                                              199            1.6 × 10.sup.6                        6      90/40/8/1   199            1.5 × 10.sup.6                        7      90/40/8/1   205            1.4 × 10.sup.6                        8      84.5/40/6.25/1                                                                            212            1.1 × 10.sup.6                        ______________________________________                                    

As evidenced by the foregoing data of Example 4 and Table II, aspolymerization temperature increases, the ratio of Al:Mg and Al:Tishould be reduced in order to obtain high catalyst efficiencies.

What is claimed is:
 1. A catalytic reaction product of (A) compound of atransition metal (TM), (B) an organomagnesium component selected from(1) an organomagnesium compound or (2) a complex of an organomagnesiumcompound and an organometallic compound in an amount sufficient tosolubilize the organomagnesium compound in hydrocarbon and (C) an activenon-metallic halide, said non-metallic halide corresponding to theformula R'X wherein R' is hydrogen or a hydrocarbyl group containing alabile halogen atom as easily lost to another compound as the chlorideatom of sec-butyl chloride and X is halogen; said reaction product beingproduced in a manner such that the organomagnesium component reacts withthe non-metallic halide to form a hydrocarbon insoluble portion, andfurther provided that sufficient aluminum, in the form of ahydrocarbylaluminum compound represented by the formula R_(3-a) AlX_(a)wherein R is hydrocarbyl, X is halide and a is a number from 0 to 1.5,is present in the catalytic reaction product in an amount sufficient toprovide a reaction product that is catalytic for the polymerization ofan α-olefin; the proportions of the foregoing components of saidcatalytic reaction product being such that the atomic ratio of Mg:TM iswithin the range from about 5:1 to about 2000:1, the atomic ratio ofX:TM is within the range from about 40:1 to about 2000:1, the atomicratio of Mg:X is within the range from about 0.2:1 to about 1:1, theatomic ratio of Mg:Al is at least 0.3:1, and the atomic ratio of Al:TMis not more than about 120:1, said reaction product being useful as acatalyst for the polymerization of an α-olefin.
 2. The reaction productof claim 1 wherein the organomagnesium compound is a dihydrocarbylmagnesium.
 3. The reaction product of claim 1 wherein theorganomagnesium component is a complex of dialkyl magnesium and atrialkyl aluminum represented by the formula MgR₂.xAlR₃ wherein R isalkyl and x is from about 0.001 to 3.3.
 4. The reaction product of claim3 wherein the atomic ratio of Mg:TM is from about 10:1 to about 60:1,the atomic ratio of Mg:X is from about 0.2:1 to about 0.7:1 and theatomic ratio of Mg to Al is from about 0.6:1 to about 7:1 for the totalcatalytic reaction product.
 5. The reaction product of claim 4 whereinthe transition metal compound is a hydrocarbyloxide of tetravalent ortrivalent titanium.
 6. The reaction product of claim 5 wherein thecatalytic reaction product is the reaction product of an alkoxide oftitanium with an intermediate reaction product of the organomagnesiumcomponent and the non-metallic halide.
 7. The reaction product of claim1 wherein the transition metal compound is tetra(alkoxy)titanium, theorganomagnesium compound is dihydrocarbyl magnesium, the organometalliccompound is trihydrocarbyl aluminum, the non-metallic halide is hydrogenhalide or a t-alkyl halide, the Mg:X ratio is from about 0.2:1 to about0.7:1, and the Mg:Al ratio is from about 0.6:1 to about 7:1, the Al:Tiratio is less than about 40:1.
 8. The reaction product of claim 7wherein the organomagnesium compound is dialkyl magnesium, and thenon-metallic halide is hydrogen chloride.
 9. The reaction product ofclaim 8 wherein the non-metallic halide is hydrogen chloride, thetetra(alkoxy)titanium is tetra(isopropoxy)titanium ortetra(butoxy)titanium, the dialkyl magnesium is dibutyl magnesium, andthe Mg:X ratio is from about 0.4:1 to 0.6:1.
 10. The reaction product ofclaim 1 or 5 wherein the atomic ratio of Mg:TM is from about 10:1 toabout 200:1, the atomic ratio of Mg:X is from about 0.4:1 to about0.6:1, the atomic ratio of X:TM is from about 40:1 to about 2000:1, theatomic ratio of Mg:Al is at least 0.3:1 and the atomic ratio of Al:TM isless than about 120:1.